KR101946776B1 - Compositon for neural layer - Google Patents

Abstract

The present application is directed to a neutral layer composition. The present application can provide a neutral layer composition capable of forming a neutral layer that can be effectively applied to the formation of a polymeric film comprising a vertically oriented self-assembled block copolymer.

Description

[0001] COMPOSITE FOR NEURAL LAYER [0002]

The present application relates to a neutral layer composition.

Block copolymers in which two or more chemically distinct polymer chains are linked by covalent bonds can be separated into regular microphases due to their self assembly properties. The fine phase separation phenomenon of such a block copolymer is generally explained by the volume fraction, the molecular weight and the mutual attraction coefficient (Flory-Huggins interaction parameter) between the constituent components, and the nanoscale spheres, cylinders, gyroid, lamella, and the like.

An important issue in the practical application of the various nanostructures formed by block copolymers is to regulate the orientation of the micro-world of block copolymers. If the spherical block copolymer nanostructure is a zero-dimensional structure having no direction of special orientation, the cylindrical or lamellar nanostructure has orientation as a one-dimensional and two-dimensional structure, respectively. The typical orientation properties of the block copolymer include a parallel orientation in which the orientation of the nanostructure is parallel to the substrate direction and a vertical orientation in which the orientation of the nanostructure is vertical to the substrate direction, Orientation is often of greater importance.

Typically, the orientation of the nanostructures in the film of the block copolymer can be determined by whether one of the blocks of the block copolymer is exposed to the surface or air. That is, the orientation of the nanostructure can be determined by selective wetting of the block. In general, since a plurality of substrates are polar and air is non-polar, a block having a larger polarity in a block copolymer is wetted on a substrate, A block with a small polarity is wetted at the interface with air, leading to a parallel orientation.

The present application provides a neutral layer composition.

The present application is directed to a neutral layer composition. The term neutral layer composition in this application may refer to a composition used in forming a neutral layer. The term neutral layer in the present application may also refer to any kind of layer capable of inducing the vertical orientation of the block copolymer.

The neutral layer composition may comprise a certain random copolymer. The random copolymer may include a unit represented by the following formula (1).

[Chemical Formula 1]

X is a single bond, an alkylene group, an oxygen atom, -C (= O) -, -OC (= O) -, -C (= O) -O- or a divalent linker represented by the following formula , And Y is a monovalent hydrocarbon group having 3 to 30 carbon atoms.

(2)

In the general formula (2), T is a divalent hydrocarbon group, and m is a number within a range of 1 to 5.

As used herein, the term single bond may mean the case where there are no separate atoms in the part. Therefore, when X is a single bond in the above formula (1), X is absent and Y is directly bonded to a benzene ring.

As used herein, unless otherwise specified, the alkylene group may mean an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be a straight, branched or cyclic alkylene group and may optionally be substituted by one or more substituents.

Unless otherwise specified, the term monovalent or divalent hydrocarbon group in the present application may mean a monovalent or divalent moiety derived from a compound or derivative of carbon and hydrogen, unless otherwise specified. Examples of the compound composed of carbon and hydrogen in the above include alkane, alkene, alkyne or aromatic hydrocarbon.

As used herein, the term alkane may mean an alkane having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms unless otherwise specified. The alkane may be linear, branched or cyclic and may optionally be substituted by one or more substituents. As the monovalent residue derived from an alkane, alkyl may be exemplified, and as the divalent residue, alkylene may be exemplified.

As used herein, unless otherwise specified, the term alkene may mean an alkene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkene may be linear, branched or cyclic and may optionally be substituted by one or more substituents. As the monovalent residue derived from alkene, alkenyl may be exemplified, and as the divalent residue, alkenylene may be exemplified.

As used herein, unless otherwise specified, the term alkyne may mean an alkyne having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkyne can be linear, branched or cyclic and optionally substituted by one or more substituents. The monovalent residue derived from alkyne may be exemplified by alkynyl, and the divalent residue may be exemplified by alkynylene.

Further, the monovalent residue derived from an aromatic hydrocarbon is referred to as an aryl in the present specification, and the divalent residue may be referred to as arylene. As used herein, the term "aryl" group or "arylene group" means, unless otherwise specified, one benzene ring structure, two or more benzene rings connected together sharing one or two carbon atoms, Or a monovalent or di-valent residue derived from a compound or a derivative thereof. The aryl group or the arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms unless otherwise specified.

In the present application, the substituent which may be optionally substituted with a substituent such as an alkane, an alkene, an alkyne, an alkyl, an alkylene, an alkenyl, an alkenylene, an alkynyl, an alkynylene, an aromatic hydrocarbon, an aryl group or an arylene group, A halogen atom such as a hydroxyl group, fluorine or chlorine, a carboxyl group, a glycidyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a thiol group, an alkyl group, An alkylene group, an alkenylene group, an alkynylene group, an alkoxy group or an aryl group, but the present invention is not limited thereto.

In the formula (1), -X-Y may be substituted at the os, meta or para positions.

Examples of the monomer capable of forming the unit of the formula (1) include 4-propylstyrene, 4-butylstyrene, 4-pentylstyrene, 4-hexylstyrene, 4-octylstyrene, 4-decylstyrene, 4-pentyloxystyrene, 4-hexyloxystyrene, 4-hexadecylstyrene, 4-octadecylstyrene, 4-propoxystyrene, 4-octadecyloxystyrene, 4-octadecyloxystyrene, 4-octadecyloxystyrene, 4-hexadecyloxystyrene, 4-octadecyloxystyrene, 4- Vinylbenzene, 1 - ((propoxy) methyl)) - 4-vinylbenzene, 1 - ((butoxy) methyl) 1 - ((hexyloxy) methyl)) - 4-vinylbenzene, 1 - ((octyloxy) methyl) - ((dodecyloxy) methyl)) -4-vinylbenzene, 1 - ((tetradecyloxy) methyl) Vinylbenzene, 1 - ((octadecyloxy) methyl)) -4-vinylbenzene or 1 - ((icosyloxy) methyl)) -4-vinylbenzene But is not limited thereto.

The random copolymer containing the unit of the formula (1) can be obtained by copolymerizing various block copolymers, for example, a block copolymer comprising units of the above-mentioned formula (1) It is possible to effectively form a neutral layer capable of inducing a neutral layer.

In the unit of the formula (1), if necessary, the benzene ring may contain one or more crosslinkable functional groups such as a hydroxyl group, an epoxy group, an isocyanate group, a glycidyl group, a substituent of the following formula (8), a benzoylphenoxy group, an alkenyloxycarbonyl group (Meth) acryloyl group or an alkenyloxyalkyl group may be substituted.

In addition, the functional group such as a hydroxyl group may be bonded to the terminal of the random copolymer containing the unit of the formula (1). The random copolymer having a hydroxyl group at its end is prepared by polymerizing a random copolymer using a RAFT (Reversible Addition Fragmentation Chain Transfer) agent or ATRP (Atom Transfer Radical polymerization) initiator having a terminal hydroxy group bonded thereto can do.

The ratio of the unit of the formula (1) in the random copolymer is not particularly limited, and the ratio can be adjusted, for example, according to the kind of the block copolymer to which the neutral layer is applied. In one example, the ratio of the units of the formula (1) in the random copolymer may be in the range of about 10 mol% to 90 mol%. In another example, the ratio may be at least 15 mol%, at least 20 mol%, at least 25 mol%, at least 30 mol%, at least 35 mol%, at least 40 mol%, or at least 45 mol% , Not more than 75 mol%, not more than 70 mol%, not more than 65 mol%, not more than 60 mol%, not more than 55 mol%, or not more than 50 mol%.

The random copolymer may contain additional units in addition to the units of formula (1). As the additional unit, for example, any one of the units represented by any one of the following formulas (3) to (7) can be exemplified.

Hereinafter, the unit represented by any one of formulas (3) to (7) may be referred to as a second unit.

(3)

In Formula (3), R is hydrogen or an alkyl group, and T is a single bond or a divalent hydrocarbon group containing or not containing a hetero atom.

[Chemical Formula 4]

R is hydrogen or an alkyl group, A is an alkylene group, R 1 may be a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group, and n is a number within a range of 1 to 3.

[Chemical Formula 5]

In Formula (5), R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group containing or not containing a hetero atom.

[Chemical Formula 6]

In Formula (6), R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and T is a divalent hydrocarbon group containing or not containing a hetero atom.

(7)

In formula 7 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 3} - or -X ₃ -C (= O) -, and wherein X ₃ is a single bond, oxygen atom, sulfur atom, -S (= O) ₂ -, and the alkylene, alkenylene or alkynylene group, R ₁ to R ₅ are each Is independently a hydrogen, an alkyl group, a haloalkyl group, a halogen atom or a crosslinkable functional group, and the number of the crosslinkable functional groups contained in R ₁ to R ₅ is one or more.

In another embodiment, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such alkyl groups may be linear, branched or cyclic and may optionally be substituted by one or more of the foregoing substituents.

The haloalkyl group in the general formula (4) is an alkyl group having at least one hydrogen atom substituted with a halogen atom, and the alkyl group is an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, . Such haloalkyl groups may be linear, branched or cyclic and may optionally be substituted by one or more of the foregoing substituents. Examples of the halogen atom substituted with a hydrogen atom in the above include fluorine or chlorine.

In another embodiment, the alkylene group of A in Formula 4 may be an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such an alkylene group may be linear, branched or cyclic and may optionally be substituted by one or more of the foregoing substituents.

The basic definitions of divalent hydrocarbon groups in formulas (3) to (7) are as described above. The divalent hydrocarbon groups represented by general formulas (3) to (7) may further include a heteroatom, if necessary. In the above, the hetero atom is a hetero atom for carbon, for example, oxygen, nitrogen or sulfur. Such a hetero atom may be included in the divalent hydrocarbon group of the formulas (3) to (7) in an amount of 1 to 4 or less.

The kind of the crosslinkable functional group contained in the above formula (7) is not particularly limited. For example, the crosslinkable functional group may be a photo-crosslinkable functional group or a heat-crosslinkable functional group. Examples of the photo-crosslinking functional group include benzoylphenoxy group, alkenyloxycarbonyl group, (meth) acryloyl group or alkenyloxyalkyl group, but are not limited thereto.

As the crosslinkable functional group which can be contained in the unit of the formula (7), for example, a functional group represented by the following formula (8) can also be used.

[Chemical Formula 8]

Y is a single bond, an alkylene group, an alkenylene group or an alkynylene group, and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -, an alkylene group, an alkenylene group, _{, -C (= O) -X 1} - or -X ₁ -C (= O) - is, in the X ₁ is a single bond, oxygen atom, sulfur _{atom, -S (= O) 2 -} , an alkylene group, An alkenylene group or an alkynylene group.

The functional group of the general formula (8) is a substituent having a terminal aziridine azide residue, and the functional group may be crosslinked.

In another embodiment, Y may be an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

In the formula (8), X may be a single bond, an oxygen atom, -C (= O) -O- or -O-C (= O) - in another example, but is not limited thereto.

Examples of the monomer capable of forming the units of the formulas (3) to (7) are not particularly limited. For example, glycidyl (meth) acrylate and the like can be exemplified as the monomer capable of forming the unit of the formula (3), and as the monomer capable of forming the unit of the formula (4), 4-vinylbenzocyclo (Meth) acrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl (meth) acrylate, 4-isocyanatobutyl acrylate and the like can be given as examples of the monomer capable of forming the unit of the formula (Meth) acrylate, and 4-isocyanatobutyl (meth) acrylate. Examples of the monomer capable of forming the unit of the formula (6) include hydroxymethyl acrylate, hydroxymethyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate (Meth) acrylate, or 6-hydroxyhexyl (meth) acrylate. Examples of the monomer capable of forming the unit of the formula (7) include a monomer having a crosslinkable functional group such as the monomer of the above formula (8), a benzoylphenoxy group, an alkenyloxycarbonyl group, a (meth) Acryloyl group, alkenyloxyalkyl group, and the like, and the like.

The ratio of the second unit in the random copolymer is not particularly limited, and the ratio can be adjusted, for example, according to the kind of the block copolymer to which the neutral layer is applied. In one example, the ratio of the second units in the random copolymer may be from about 1 mole% to about 20 mole%, but is not limited thereto. In another example, the ratio may be about 18 mol% or less, about 16 mol% or less, about 14 mol% or less, about 12 mol% or less, about 10 mol% or less, about 8 mol% or about 6 mol% or about 4 mol% or less.

The random copolymer may include an additional unit (hereinafter referred to as a third unit) together with the unit of the formula (1) and the second unit. As the third unit, there may be mentioned (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylic acid ester compound such as methyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate or octyl Vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, And styrene monomers such as styrene, 4-fluorostyrene, and the like are exemplified, but the present invention is not limited thereto.

In one example, the random copolymer may further include a unit represented by the following general formula (9) as the third unit.

[Chemical Formula 9]

In Formula (9), R ₁ is hydrogen or an alkyl group, and R ₂ is an alkyl group.

In the formula (9), R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms in another example; Hydrogen or a methyl group; Or a methyl group.

In another embodiment, R ₂ may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

The above-mentioned predetermined monomer-derived polymerization unit may mean a skeleton structure formed by polymerization of each of the monomers described above in the random copolymer.

When the third unit is included in the random copolymer, the ratio is. And is not particularly limited, and it can be adjusted, for example, according to the kind of the block copolymer to which the neutral layer is applied. In one example, the ratio of the third unit in the random copolymer may be about 10 mol% to about 90 mol%, but is not limited thereto. In another example, the ratio may be at least about 15 mole percent, at least 20 mole percent, at least 25 mole percent, at least 30 mole percent, at least 35 mole percent, at least 40 mole percent, or at least 45 mole percent, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, or 55 mol% or less.

The number average molecular weight (Mn) of the random copolymer may be in the range of, for example, 2,000 to 500,000. The number average molecular weight may be 3,000 or more, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, 20,000 or more, 30,000 or more, 40,000 or more, 50,000 or more, , 80,000 or more, 90,000 or more, or about 100,000 or more. The number average molecular weight may be about 400,000 or less, about 300,000 or less, or about 200,000 or less in another example. In the present specification, the term number average molecular weight is a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight means number average molecular weight unless otherwise specified. The molecular weight of the random copolymer can be adjusted in consideration of the physical properties and the like of the neutral layer including the random copolymer.

The method of producing such a random copolymer is not particularly limited. For example, the random copolymer may be prepared by applying a free radical polymerization method or an LRP (Living Radical Polymerization) method. Examples of the LRP method include anion polymerization in which polymerization is carried out in the presence of an inorganic acid salt or an organic aluminum compound such as an alkali metal or an alkaline earth metal salt using an organic rare earth metal complex or an organic alkali metal compound as an initiator, (ATRP), which utilizes an atom transfer radical polymerization agent, and ARGET (Activators Regenerated by Electron), which uses an atom transfer radical polymerization agent as a polymerization initiator and undergoes polymerization under an organic or inorganic reducing agent that generates electrons, Transfer (ATRP), Initiators for Continuous Activator Regeneration (ICAR) Atom Transfer Radical Polymerization, Reversible Addition Reversible Addition Separate-cleavage chain transfer (RAFT) or organic A method of using a tellurium compound as an initiator, and the like can be exemplified , A suitable method may be employed in the method.

The kind of the radical initiator that can be used in the polymerization process is not particularly limited. For example, an azo initiator such as AIBN (azobisisobutyronitrile) or 2,2'-azobis- (2,4-dimethylvaleronitrile) or an azo initiator such as benzoyl peroxide or di-tert-butyl peroxide (DTBP), and the like may be used. For example, depending on the type of the monomer, such as the method using the thermal self-initiation of the styrenic monomer A polymerization method that does not use an initiator may be applied.

The polymerization process can be carried out, for example, in a suitable solvent, and in this case, applicable solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, , But are not limited to, solvents such as chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide, dimethylsulfoxide or dimethylacetamide. After the formation of the random copolymer, a random copolymer can be obtained by precipitation using a non-solvent. Examples of the non-solvent which can be used here include alcohols such as methanol, ethanol, n-propanol or isopropanol, And ether solvents such as glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, but are not limited thereto.

In the field of polymer synthesis, a method of producing a polymer by performing polymerization according to a monomer forming the polymer is known, and any of the above methods can be applied to the production of the random copolymer of the present application.

The neutral layer composition containing the random copolymer as described above may contain only the predetermined random copolymer or may appropriately contain other components than the random copolymer, if necessary. The neutral layer composition may comprise at least the above-mentioned random copolymer as a main component. The inclusion of the main component in the present specification means that the composition contains only the random copolymer or contains at least about 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt% 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more. The ratio may be from about 100% by weight or less to about 99% by weight or less in another example. Other components that can be included with the random copolymer include, for example, thermal initiators or photoinitiators necessary when the random copolymer includes the above-described photo-crosslinkable or heat-crosslinkable functional groups.

The present application is also directed to a neutral layer comprising the random copolymer. The term neutral layer in the present application means a layer capable of inducing the vertical orientation of the block copolymer as described above.

The neutral layer may be formed on a suitable substrate. The substrate on which the neutral layer is formed is exemplified by a silicon wafer, a silicon oxide substrate, a silicon nitride substrate, or a crosslinked PET (poly (ethylene terephthalate)) film.

The neutral layer can be formed using the neutral layer composition described above. For example, the formation process of the neutral layer may include coating the neutral layer composition on the substrate and fixing the layer of the coated neutral layer composition. The method for coating the neutral layer composition on the substrate is not particularly limited. For example, a method such as bar coating, spin coating or comma coating may be applied, and coating by a roll-to-roll method may be applied have.

The method of fixing the layer of the neutral layer composition is not particularly limited. For example, a method of inducing covalent bonding between the layer and the substrate by an appropriate method, or inducing a chemical crosslinking reaction in the layer Etc. may be applied. For example, when the above process is performed by heat treatment, the heat treatment may be adjusted within a range of about 100 ° C to 250 ° C or about 100 ° C to 200 ° C. Also, the time required for the heat treatment may be changed as needed, and may be adjusted within a range of, for example, about 1 minute to 72 hours or about 1 minute to 24 hours. The temperature and time of the heat treatment may be adjusted to an appropriate level in consideration of the type of the functional group of the random copolymer of the neutral layer composition.

The neutral layer may have a thickness of, for example, about 2 nm to 100 nm, and in another example, it may have a thickness of about 2 nm to 50 nm. Within this thickness range, the surface uniformity of the neutral layer can be maintained, leading to the vertical orientation of the block copolymer and thereafter being advantageous in not hurting etch selectivity during the etching process.

The present application is also directed to a polymeric membrane comprising a neutral layer comprising the random copolymer and a block copolymer formed on one side of the neutral layer and having a first block and a second block chemically distinct from the first block, To the laminate.

The polymer membrane may be used in various applications such as various electronic or electronic devices, a process of forming the pattern or a recording medium such as a magnetic storage medium or a flash memory, a biosensor, Manufacturing process, and the like.

In one example, the block copolymer in the polymer membrane may be self-assembled to implement a cyclic structure including a sphere, a cylinder, a gyroid or a lamellar, . In the case of spores or lamellas of the above structures, the block copolymer may be present in a vertically oriented state.

For example, within the segment of the first or second block or another block covalently bonded thereto in the block copolymer, the other segment may be vertically oriented, forming a regular structure such as a lamellar shape or a cylinder shape.

The block copolymer that can be included in the polymer membrane in the above-described laminate is not particularly limited.

For example, the block copolymer may include a repeating unit represented by the above-mentioned formula (1) as the first block.

The kind of the second block included in the block copolymer together with the first block is also not particularly limited. For example, the second block may include a polystyrene block such as a polyvinyl pyrrolidone block, a polylactic acid block, a polyvinyl pyridine block, polystyrene or poly trimethylsilyl styrene, a poly Poly (perfluorostyrene) blocks such as poly (methylstyrene) and poly (methylstyrene) blocks such as poly (methyl acrylate) (Meth) acrylate block, a polyalkylene oxide block such as polyethylene oxide, a polybutadiene block, a polyisoprene block, or a polyolefin block such as polyethylene. have.

As the second block, a block including the units of the formulas (3) to (7) and / or the unit of the formula (9) described above may be used.

The block copolymer of the present application may be a diblock copolymer including the above-mentioned first block and second block, or may include at least one of the first block and the second block, ≪ / RTI >

The number average molecular weight (Mn) of the block copolymer may be in the range of, for example, 2,000 to 500,000. The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.50.

In this range, the block copolymer can exhibit proper self-assembling properties. The number average molecular weight of the block copolymer and the like can be adjusted in consideration of the desired self-assembling structure and the like.

When the block copolymer contains at least the first and second blocks, the ratio of the first block in the block copolymer, for example, the block including the unit of the above-mentioned formula (1), is 10 mol% to 90 mol % ≪ / RTI >

A specific method for producing the block copolymer in the present application is not particularly limited as long as it includes the step of forming at least one block of the block copolymer using the above-mentioned monomer.

For example, the block copolymer can be prepared by the LRP (Living Radical Polymerization) method using the above monomers. For example, anionic polymerization in which an organic rare earth metal complex is used as a polymerization initiator, or an organic alkali metal compound is used as a polymerization initiator in the presence of an inorganic acid salt such as a salt of an alkali metal or an alkaline earth metal, An atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization initiator, and an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Initiators for Continuous Activator Regeneration (ATR), Atomic Transfer Radical Polymerization (ATRP), Inorganic Reducing Agent Reversible Additive - Reversible addition-cleavage chain transfer using cleavage chain transfer agent And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

For example, the block copolymer can be prepared in a manner that includes polymerizing a reactant containing monomers capable of forming the block in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization .

The method of forming the other block included in the copolymer together with the block formed by using the monomer in the production of the block copolymer is not particularly limited and may be appropriately selected in consideration of the kind of the desired block, Block can be formed.

The preparation of the block copolymer may further include, for example, a step of precipitating the polymerization product produced through the above process in the non-solvent.

The kind of the radical initiator is not particularly limited and may be appropriately selected in consideration of the polymerization efficiency. For example, AIBN (azobisisobutyronitrile) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2 ' -azobis- (2,4-dimethylvaleronitrile), and peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP).

The living radical polymerization process can be carried out in the presence of a base such as, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, Amide, dimethylsulfoxide or dimethylacetamide, and the like.

Examples of the non-solvent include ethers such as alcohols such as methanol, ethanol, n-propanol or isopropanol, glycols such as ethylene glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, But is not limited thereto.

There is no particular limitation on the method for forming a polymer film as described above using a block copolymer. For example, the method may include forming the polymer membrane including the block copolymer in a self-assembled state on the neutral layer. For example, the method may include forming a layer of the block copolymer or a coating liquid in which the block copolymer is diluted with an appropriate solvent on the neutral layer by applying or the like, and if necessary, matured or heat-treat the layer.

The aging or heat treatment may be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and may be performed at, for example, the glass transition temperature or a temperature higher than the phase transition temperature. The time at which this heat treatment is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed if necessary. The heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used.

The formed layer may be solvent aged for about 1 minute to 72 hours in a non-polar solvent and / or a polar solvent at room temperature in another example.

The present application also relates to a method of pattern formation. The method may include, for example, selectively removing the first or second block of the block copolymer from the polymer membrane of the laminate. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymeric film comprising the block copolymer on a substrate, selectively removing one or more blocks of the block copolymer present in the film, and then etching the substrate . In this way, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation. The type of the substrate to be applied to this method is not particularly limited and may be selected as required. For example, silicon oxide or the like may be applied.

For example, the method can form a nanoscale pattern of silicon oxide that exhibits a high aspect ratio. For example, the polymer film is formed on silicon oxide, and one block of the block copolymer is selectively removed while the block copolymer in the polymer film forms a predetermined structure. Thereafter, the silicon oxide is removed in various ways, for example, , Reactive ion etching, or the like to form various patterns including patterns of nano-rods or nano holes. In addition, it is possible to realize a nano pattern having a large aspect ratio through such a method.

For example, the pattern can be implemented in a scale of several tens of nanometers, and such a pattern can be utilized for various purposes including, for example, a next-generation information electronic magnetic recording medium and the like.

The method of selectively removing one block of the block copolymer in the above method is not particularly limited. For example, a method of removing a relatively soft block by irradiating an appropriate electromagnetic wave, for example, ultraviolet light, Can be used. In this case, the ultraviolet ray irradiation conditions are determined depending on the type of the block of the block copolymer, and can be performed, for example, by irradiating ultraviolet light having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, the ultraviolet irradiation may be followed by a step of treating the polymer membrane with an acid or the like to further remove the segment decomposed by ultraviolet rays.

The step of selectively etching the substrate using the polymer film having the removed block as a mask is not particularly limited and may be performed through a reactive ion etching step using, for example, CF ₄ / Ar ions or the like, And then removing the polymer membrane from the substrate by an oxygen plasma treatment or the like.

The present application can provide a neutral layer composition capable of forming a neutral layer that can be effectively applied to the formation of a polymeric film comprising a vertically oriented self-assembled block copolymer.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 and Fig. 2 show the results of orientation of block copolymers in Comparative Examples and Examples. Fig.

Hereinafter, the present application will be described in detail by way of examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

1. NMR measurement

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The analytes were diluted to a concentration of about 10 mg / ml in a solvent for NMR measurement (CDCl ₃ ), and chemical shifts were expressed in ppm.

<Application Abbreviation>

br = broad signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = double triplet, q = quartet, p = octet, m = polyline.

2. Gel Permeation Chromatograph (GPC)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel Permeation Chromatography). Add a sample to be analyzed such as a block copolymer or a macroinitiator of the example or comparative example into a 5 mL vial and dilute with tetrahydrofuran (THF) to a concentration of about 1 mg / mL. After that, the calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. The analytical program used was a ChemStation from Agilent Technologies. The elution time of the sample was compared with a calibration curve to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the molecular weight distribution (PDI ) Were calculated. The measurement conditions of GPC are as follows.

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

Standard samples: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Production Example 1. Synthesis of Compound (A)

In the following formula (A), X is a residue of the following formula (B), T in the formula (B) is methylene, m is 1, and Y in the formula (A) is a dodecyl group Respectively. T in formula (B) is linked to the benzene ring and the oxygen atom is linked to Y, i.e., the dodecyl group. 4-chloromethylstyrene (22.1 g, 144.8 mmol) and 1-dodecanol (30.0 g, 160.1 mmol) were dissolved in 300 mL tetrahydrofuran (THF) And the temperature was lowered to 0 ° C. Sodium hydride (NaH) (7.7 g, 320.8 mmol) was added in small portions and stirred for 1 hour, then heated to 70 &lt; 0 &gt; C and allowed to react for 24 hours. At the end of the reaction, the reaction mixture was cooled to room temperature, and a small amount of water was added to the ice water to react with remaining sodium hydride. After removing the reaction solvent, tetrahydrofuran, the organic layer was collected by extraction with dichloromethane (DCM) / secondary pure water. The resulting compound was purified by column chromatography using hexane / dichloromethane as a mobile phase, Compound (A) (23.9 g, 79.0 mmol) was obtained.

&Lt; NMR analysis result >

_{^{1 H-NMR (CDCl 3)}} : δ7.39 (dd, 2H); [delta] 7.30 (dd, 2H); [delta] 6.71 (dd, 1H); [delta] 5.74 (d, IH); [delta] 5.23 (d, IH); [delta] 4.49 (s, 2H); [delta] 3.46 (t, 2H); delta 1.61 (p, 2H); [delta] 1.37-1.26 (m, 16H); [delta] 0.89 (t, 3H).

(A)

[Chemical Formula B]

Production Example 2. Synthesis of block copolymer (A)

(Number average molecular weight (Mn): 8500, molecular weight distribution (Mw), molecular weight distribution (Mw), and molecular weight distribution (Mw) were obtained by reacting azobisisobutyronitrile (AIBN) and RAFT reagent (CPDB, 2-cyanoprop- / Mn): 1.16) was synthesized. The synthesized macromonomer and the compound (A) and the azobisisobutyronitrile (AIBN) were diluted in anisole at an equivalent ratio of 1: 100: 0.5 (macromonomer: Compound (A): AIBN) &Lt; / RTI &gt; Thereafter, the mixture was allowed to react at 70 DEG C in a nitrogen atmosphere for 4 hours to obtain a block copolymer (A). The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the block copolymer (A) were 14800 and 1.16, respectively. In the block copolymer, the repeating unit derived from the methyl methacrylate and the repeating unit derived from the compound A, i.e., -XY in the formula (1) of the formula (1) is connected to the para position, X is a unit of the formula , T is methylene, m is 1, Y is a dodecyl group (T in formula (2) is connected to a benzene ring, and the oxygen atom is linked to Y, i.e., a dodecyl group).

Production Example 3. Synthesis of random copolymer (B)

The random copolymer (B) for neutral layer was synthesized by using methyl methacrylate (MMA), the compound (A) and glycidyl methacrylate (GMA). MMA, Compound (A), GMA and AIBN were diluted in anisole at an equivalent ratio of 50: 48: 2: 0.5 (MMA: Compound (A): GMA: AIBN) Solution. Thereafter, the mixed solution was reacted at 60 DEG C in a nitrogen atmosphere for 10 hours to obtain a random copolymer (B). The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the random copolymer (B) were 106600 and 2.50, respectively.

Comparative Example 1

Self-assembly of the block copolymer (A)

A self-assembled polymer membrane was formed using the block copolymer (A) of Production Example 2 and the results were confirmed. Specifically, the copolymer was dissolved in toluene at a concentration of about 1.0% by weight, and the resulting coating solution was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds and then subjected to thermal annealing at about 160 캜 To form a membrane comprising the self-assembled block copolymer. 1 is an SEM image of the polymer membrane formed as described above. It can be confirmed from the figure that the orientation of the polymer film is not properly performed.

Example 1.

The self-assembling of the block copolymer (A) into which the neutral layer of the random copolymer (B)

Using the random copolymer (B) of Production Example 3 and the block copolymer (A) of Production Example 2, crosslinked neutral layers and self-assembled polymer membranes were formed and their results were confirmed. Specifically, the random copolymer (B) of Production Example 3 was first dissolved in toluene at a concentration of about 1.0% by weight, the resulting coating liquid was spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, To form a crosslinked neutral layer through thermal crosslinking. The block copolymer (A) was dissolved in toluene at a concentration of about 1.0 wt.%, And the prepared coating solution was spin-coated on the neutral layer at a speed of 3000 rpm for 60 seconds and then subjected to thermal annealing ) To form a membrane comprising the self-assembled block copolymer. 2 is an SEM image of the polymer membrane formed as described above. It can be seen from the figure that an appropriate lamellar vertical alignment structure is formed.

Claims (14)

A neutral layer composition comprising a random copolymer comprising a unit of the following formula (1) and a second unit represented by any one of the following formulas (3), (5) and (7)
[Chemical Formula 1]

X is an oxygen atom, -C (= O) -, -OC (= O) -, -C (= O) -O- or a divalent linker represented by the following formula (2) 30 is a monovalent hydrocarbon group:
(2)

T in the formula (2) is a divalent hydrocarbon group, and m is a number within the range of 1 to 5:
(3)

In Formula (3), R is hydrogen or an alkyl group, and T is a single bond or a divalent hydrocarbon group containing or not containing a hetero atom:
[Chemical Formula 5]

In formula (5), R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group containing or not containing a hetero atom.
(7)

In formula 7 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 3} - or -X ₃ -C (= O) -, and wherein X ₃ is a single bond, oxygen atom, sulfur atom, -S (= O) ₂ -, and the alkylene, alkenylene or alkynylene group, R ₁ to R ₅ are each Is independently a hydrogen, an alkyl group, a haloalkyl group, a halogen atom or a crosslinkable functional group, and the number of the crosslinkable functional groups contained in R ₁ to R ₅ is one or more. The neutral layer composition according to claim 1, wherein the ratio of the units of formula (1) in the random copolymer is in the range of 10 mol% to 90 mol%. delete The neutral layer composition according to claim 1, wherein the unit of the formula (1) is substituted with a crosslinkable functional group. The neutral layer composition according to claim 1, wherein the random copolymer further comprises a polymerization unit derived from a (meth) acrylic acid ester compound, a polymerization unit derived from vinylpyridine, or a polymerization unit derived from a styrene monomer. 2. The neutral layer composition of claim 1, wherein the random copolymer further comprises a unit of the following formula:
[Chemical Formula 9]

In Formula (9), R ₁ is hydrogen or an alkyl group, and R ₂ is an alkyl group. The neutral layer composition according to claim 1, wherein the random copolymer has a number average molecular weight in the range of 2000 to 500000. A neutral layer comprising a random copolymer comprising a unit of the following formula (1) and a second unit represented by any one of the following formulas (3), (5) and (7)
[Chemical Formula 1]

X is a single bond, an alkylene group, an oxygen atom, -C (= O) -, -OC (= O) -, -C (= O) -O- or a divalent linker represented by the following formula , And Y is a monovalent hydrocarbon group having 3 to 30 carbon atoms:
(2)

T in the formula (2) is a divalent hydrocarbon group, and m is a number within the range of 1 to 5:
(3)

In Formula (3), R is hydrogen or an alkyl group, and T is a single bond or a divalent hydrocarbon group containing or not containing a hetero atom:
[Chemical Formula 5]

In formula (5), R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group containing or not containing a hetero atom.
(7)

In formula 7 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 3} - or -X ₃ -C (= O) -, and wherein X ₃ is a single bond, oxygen atom, sulfur atom, -S (= O) ₂ -, and the alkylene, alkenylene or alkynylene group, R ₁ to R ₅ are each Is independently a hydrogen, an alkyl group, a haloalkyl group, a halogen atom or a crosslinkable functional group, and the number of the crosslinkable functional groups contained in R ₁ to R ₅ is one or more.  A method of forming a neutral layer, comprising: coating the neutral layer composition of claim 1 on a substrate; and fixing the layer of the coated neutral layer composition. A neutral layer of claim 8; And a polymeric film formed on one surface of the neutral layer, the polymeric film having a first block and a second block chemically distinguished from the first block. 11. The laminate according to claim 10, wherein the block copolymer embodies a sphere, cylinder, gyroid or lamellar structure. The laminate according to claim 10, wherein the first block of the block copolymer comprises a unit represented by the following formula
[Chemical Formula 1]

X is a single bond, an alkylene group, an oxygen atom, -C (= O) -, -OC (= O) -, -C (= O) -O- or a divalent linker represented by the following formula , And Y is a monovalent hydrocarbon group having 3 to 30 carbon atoms:
(2)

In the general formula (2), T is a divalent hydrocarbon group, and m is a number within a range of 1 to 5. A neutral layer of claim 8; And forming a polymeric film formed on one surface of the neutral layer, the polymeric film having a first block and a second block chemically distinguished from the first block in a self-assembled state, &Lt; / RTI &gt; 14. A pattern forming method comprising the step of selectively removing a first or second block of a block copolymer in a polymer film of the laminate of claim 13.

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